CN116987229A - Photo-curing material and preparation method and application thereof - Google Patents
Photo-curing material and preparation method and application thereof Download PDFInfo
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- CN116987229A CN116987229A CN202310804329.2A CN202310804329A CN116987229A CN 116987229 A CN116987229 A CN 116987229A CN 202310804329 A CN202310804329 A CN 202310804329A CN 116987229 A CN116987229 A CN 116987229A
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- acrylamide
- photo
- reactive
- polyurethane
- monomer
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- 239000000463 material Substances 0.000 title claims abstract description 135
- 238000000016 photochemical curing Methods 0.000 title abstract description 60
- 238000002360 preparation method Methods 0.000 title abstract description 19
- 239000000178 monomer Substances 0.000 claims abstract description 60
- 239000004814 polyurethane Substances 0.000 claims abstract description 59
- 229920002635 polyurethane Polymers 0.000 claims abstract description 59
- 239000002994 raw material Substances 0.000 claims abstract description 28
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 claims abstract description 14
- 239000000654 additive Substances 0.000 claims abstract description 3
- 230000000996 additive effect Effects 0.000 claims abstract description 3
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 claims description 41
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 37
- 239000003795 chemical substances by application Substances 0.000 claims description 37
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 20
- 238000010146 3D printing Methods 0.000 claims description 19
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 15
- 238000006116 polymerization reaction Methods 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 11
- -1 acrylic ester Chemical class 0.000 claims description 11
- 239000002981 blocking agent Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 8
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- UUORTJUPDJJXST-UHFFFAOYSA-N n-(2-hydroxyethyl)prop-2-enamide Chemical compound OCCNC(=O)C=C UUORTJUPDJJXST-UHFFFAOYSA-N 0.000 claims description 5
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 claims description 3
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 claims description 3
- XHULUQRDNLRXPF-UHFFFAOYSA-N 3-ethenyl-1,3-oxazolidin-2-id-4-one Chemical compound C(=C)N1[CH-]OCC1=O XHULUQRDNLRXPF-UHFFFAOYSA-N 0.000 claims description 3
- FOFGHOIKFUUAPZ-UHFFFAOYSA-N 3-ethenyl-5-methyl-1,3-oxazolidin-2-id-4-one Chemical compound C(=C)N1[CH-]OC(C1=O)C FOFGHOIKFUUAPZ-UHFFFAOYSA-N 0.000 claims description 3
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 3
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 claims description 3
- WXFIFTYQCGZRGR-UHFFFAOYSA-N 5-hydroxy-2-methylhex-2-enamide Chemical compound CC(O)CC=C(C)C(N)=O WXFIFTYQCGZRGR-UHFFFAOYSA-N 0.000 claims description 3
- FXIVKZGDYRLHKF-UHFFFAOYSA-N C(C)OP(OC(C1=C(C=C(C=C1C)C)C)=O)(=O)C1=CC=CC=C1 Chemical compound C(C)OP(OC(C1=C(C=C(C=C1C)C)C)=O)(=O)C1=CC=CC=C1 FXIVKZGDYRLHKF-UHFFFAOYSA-N 0.000 claims description 3
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 3
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 claims description 3
- DZHSVSBJDNJICY-UHFFFAOYSA-N bis(4-methylphenyl)phosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound C1=CC(C)=CC=C1P(=O)(C=1C=CC(C)=CC=1)C(=O)C1=C(C)C=C(C)C=C1C DZHSVSBJDNJICY-UHFFFAOYSA-N 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 239000003112 inhibitor Substances 0.000 claims description 3
- 239000012948 isocyanate Substances 0.000 claims description 3
- 150000002513 isocyanates Chemical class 0.000 claims description 3
- MVBJSQCJPSRKSW-UHFFFAOYSA-N n-[1,3-dihydroxy-2-(hydroxymethyl)propan-2-yl]prop-2-enamide Chemical compound OCC(CO)(CO)NC(=O)C=C MVBJSQCJPSRKSW-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- 229920005862 polyol Polymers 0.000 claims description 3
- 150000003077 polyols Chemical class 0.000 claims description 3
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims description 3
- NWWQVENFTIRUMF-UHFFFAOYSA-N diphenylphosphanyl 2,4,6-trimethylbenzoate Chemical compound CC1=CC(C)=CC(C)=C1C(=O)OP(C=1C=CC=CC=1)C1=CC=CC=C1 NWWQVENFTIRUMF-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002861 polymer material Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 27
- 238000001723 curing Methods 0.000 description 25
- 239000012752 auxiliary agent Substances 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 14
- 238000007334 copolymerization reaction Methods 0.000 description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 13
- 230000000694 effects Effects 0.000 description 13
- 229910052760 oxygen Inorganic materials 0.000 description 13
- 239000001301 oxygen Substances 0.000 description 13
- 230000008569 process Effects 0.000 description 11
- 238000007639 printing Methods 0.000 description 10
- 230000009477 glass transition Effects 0.000 description 9
- 150000001412 amines Chemical class 0.000 description 8
- 230000005764 inhibitory process Effects 0.000 description 8
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000006229 carbon black Substances 0.000 description 6
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 6
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical group O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 238000011417 postcuring Methods 0.000 description 5
- CFXCGWWYIDZIMU-UHFFFAOYSA-N Octyl-3,5-di-tert-butyl-4-hydroxy-hydrocinnamate Chemical compound CCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 CFXCGWWYIDZIMU-UHFFFAOYSA-N 0.000 description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000012975 dibutyltin dilaurate Substances 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 3
- 150000001408 amides Chemical group 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- JSYQTJCNKUAUMM-UHFFFAOYSA-N ethyl carbamate;prop-2-enamide Chemical compound NC(=O)C=C.CCOC(N)=O JSYQTJCNKUAUMM-UHFFFAOYSA-N 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- NDKUQUPCEFPMSK-UHFFFAOYSA-N 1-ethenylpyrrolidin-2-one;prop-2-enamide Chemical compound NC(=O)C=C.C=CN1CCCC1=O NDKUQUPCEFPMSK-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000001953 sensory effect Effects 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 150000003926 acrylamides Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Ceramic Engineering (AREA)
- Civil Engineering (AREA)
- Composite Materials (AREA)
- Structural Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The application discloses a photo-curing material, a preparation method and application thereof, and belongs to the technical field of high polymer materials. The raw materials of the photo-curing material comprise the following components: 50-80 parts of polyurethane oligomer; 20-40 parts of reactive monomer; 1-10 parts of reactive photosensitive auxiliary; 0.5-3 parts of photoinitiator; wherein the monomer structure of the reactive photosensitive additive comprises a maleimide structure. The surface adhesiveness of the product prepared by the photo-curing material is obviously improved, and the comprehensive mechanical property of the product is obviously improved.
Description
Technical Field
The application belongs to the technical field of high polymer materials, and particularly relates to a photo-curing material, a preparation method and application thereof.
Background
Photo-curing 3D printing technology is becoming increasingly accepted because of its ability to print complex three-dimensional structures with high efficiency and accuracy. Polyurethane (Polyurethane) refers to a class of polymers that contain urethane characteristic units in the backbone. Such polymer materials are widely used in various fields due to their excellent properties. Several attempts have been made to apply polyurethane to photo-cured 3D printing materials, but satisfactory results have not been obtained.
The prior art discloses a photo-curing resin composition with rubber elasticity, which is composed of monomers and oligomers with low glass transition temperature, ensures high flexibility and extensibility, can well control stress deformation of a cured product and ensures the strength of the cured product. However, it was found that the surface of the finished print produced in a similar one-component system would be tacky when it is actually used because the free radical reaction is very oxygen sensitive and the oxygen rich environment may retard the free radical polymerization reaction, resulting in a lower degree of polymerization (curing) of the finished print surface and more liquid resin remaining, and thus tacky. For the bottom-up photocuring 3D printing process, the liquid resin reacts at the bottom of the trough to generate photocuring, and the bottom of the trough does not have enough oxygen, so the problems are avoided. However, when printing is completed, the post-treatment process is usually carried out in air, and the presence of oxygen causes a relatively serious problem of polymerization inhibition and surface tackiness.
In the preparation of common UV materials, in order to solve the problem of oxygen inhibition and stickiness, one or more technical means of polyurethane acrylamide oligomer, acrylamide diluent and active amine auxiliary agent are generally adopted to overcome oxygen inhibition and improve the photo-curing rate; however, during 3D printing, the critical transmission depth of the material may be greater than the thickness of the printed layer. Too fast a cure rate can result in semi-cured material on the surface of the printed product, which is difficult to clean, aggravates product tackiness, and at the same time, too fast a reaction rate, photo-thermal side reactions can result in reduced usage of the liquid material during continuous printing. Thus, there is a need to address the contradiction between surface tackiness and cure rate of 3D printed products.
Disclosure of Invention
In view of the above, the application provides a photo-curing material, a preparation method and application thereof, and aims to solve the technical problem that the surface of an element prepared by using the photo-curing material is sticky.
In one aspect, the application provides a light-cured material, which comprises the following raw materials in parts by weight:
50-80 parts of polyurethane oligomer;
20-40 parts of reactive monomer;
1-10 parts of a reactive photosensitive auxiliary;
0.5-3 parts of photoinitiator;
wherein the reactive photosensitive aid comprises a maleimide structure-containing material.
The application innovatively adds the reactive photosensitive auxiliary agent into the raw material of the photo-curing material, and the reactive photosensitive auxiliary agent mainly comprises a material containing a maleimide structure, and the material with the structure has excellent copolymerization reaction rate and high melting point when participating in copolymerization reaction, can effectively participate in copolymerization reaction of polyurethane oligomer, improves the conversion rate of the material, improves the glass transition temperature of the material, and improves the surface stickiness phenomenon.
Optionally, a phenyl group is attached to the maleimide-containing structure.
The chemical structure of the reactive photosensitive auxiliary agent further selected by the application contains maleimide and benzene ring structures; the benzene ring structure can absorb ultraviolet light, reduce the transmission depth of the photo-curing material, reduce the phenomenon of semi-curing gel on the surface of a photo-curing material product and improve the phenomenon of surface stickiness.
Optionally, a phenyl group is attached to the nitrogen atom in the maleimide structure.
Optionally, the reactive photosensitive aid is selected from at least one of N-phenylmaleimide (NPMI), N ' -4,4' -diphenylmethane Bismaleimide (BDM), N ' -m-phenylene bismaleimide (PDM), and derivatives thereof.
Alternatively, the reactive photo-sensitive aid is preferably N-phenylmaleimide (NPMI).
The application further selects N-phenylmaleimide (NPMI) as a reactive photosensitive auxiliary agent, because the NPMI is a crystalline monomer which has an extremely high melting point of 88-90 ℃; because NPMI is extremely easy to crystallize and has high melting point, residual NPMI monomer on the surface of a printed product can form crystals, and the surface stickiness of the material can be further improved.
Optionally, the reactive monomer is selected from at least one of N-vinyl pyrrolidone, N-vinyl caprolactam, N-vinyl oxazolidone, N-vinyl methyl oxazolidone, and acryloylmorpholine.
The reactive monomer of the application adopts the monomer with amide structure, the curing rate of the acrylamide monomer is high, and the acrylamide monomer has high glass transition temperature, and can effectively raise the glass transition temperature of the cured material after the acrylamide monomer participates in copolymerization, thereby further achieving the effect of improving the sticky phenomenon of the product surface.
Optionally, the polyurethane oligomer is selected from polyurethane acrylate oligomers and/or polyurethane acrylamide oligomers.
Optionally, the raw materials of the polyurethane oligomer comprise the following components: isocyanate, polyol, catalyst, end-capping agent and polymerization inhibitor.
Optionally, the preparation method of the polyurethane oligomer comprises the following steps: mixing the raw materials, and reacting at 60-80 ℃ to obtain the polyurethane oligomer.
Alternatively, the capping agent is selected from hydroxyl-bearing (meth) acrylamide-based capping agents or hydroxyl-bearing (meth) acrylate capping agents.
The end capping agent of the application adopts polyurethane oligomer synthesized by (methyl) acrylamide end capping agent with hydroxyl as polyurethane acrylamide oligomer; the blocking agent monomer can overcome the problem of oxygen polymerization inhibition and stickiness, and has high polymerization speed, so that the stickiness phenomenon of the surface of the photo-curing material product can be further improved.
The end capping agent disclosed by the application is a (methyl) acrylic ester end capping agent with hydroxyl, the synthesized polyurethane oligomer is polyurethane acrylic ester oligomer, and the problem of stickiness of a polyurethane acrylic ester system can be improved when the polyurethane acrylic ester oligomer and an acrylamide reactive monomer are copolymerized.
Optionally, the hydroxyl-bearing (meth) acrylamide-based capping agent is selected from at least one of N- (hydroxymethyl) acrylamide, N-hydroxyethyl acrylamide, N- [ tris (hydroxymethyl) methyl ] acrylamide, 2-hydroxypropyl methacrylamide.
Optionally, the (methyl) acrylic ester end-capping agent with hydroxyl is at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate and butyl ester end-capping agent.
Optionally, the photoinitiator is selected from at least one of diphenyl- (2, 4, 6-trimethylbenzoyl) phosphorus oxide, phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide, ethyl 2,4, 6-trimethylbenzoyl phenylphosphonate, and 2,4, 6-trimethylbenzoyl-di (p-tolyl) phosphine oxide.
Optionally, the polyurethane oligomer is selected from any value or range of values between any two of 50, 55, 60, 65, 70, 75, 80 by weight.
Optionally, the parts by weight of the reactive monomer is selected from any value or range of values between any two of 20, 25, 30, 35, 40.
Optionally, the weight portion of the reactive photosensitive additive is selected from any value or range value between any two of 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10.
Optionally, the weight portion of the photoinitiator is selected from any value or range of values between any two of 0.5, 1, 1.5, 2, 2.5, 3.0.
Optionally, the raw materials of the photo-curing material further comprise an antioxidant (such as 1135) and/or carbon black (N30).
In a second aspect, the present application provides a method for preparing the above-mentioned photocurable material, said method comprising the steps of:
s1: preparing raw materials according to a raw material formula;
s2: and stirring and mixing the polyurethane oligomer, the reactive monomer, the reactive photosensitive auxiliary and the photoinitiator to obtain the light-cured material.
In the preparation method of the photo-curing material, the raw materials are mixed at normal temperature or room temperature.
In a third aspect, the present application provides the use of the above photo-curable material in a 3D printing material.
The light-cured material has the advantages of high curing rate, excellent performance and no stickiness on the surface of a product, and can be used in various fields, in particular to the field of 3D printing.
In a fourth aspect, the present application provides a 3D printed product, wherein the material of the 3D printed product is the above photo-curing material.
After the photocuring material is used for photocuring 3D printing, the obtained printing piece is placed into water for post-curing reaction. Because the reactive monomer, the end capping agent and the active hydrogen containing amine in the reactive photosensitive auxiliary agent in the photocuring raw material can be used as electron donors, the activity of the radical annihilated by oxygen can be recovered, and the problem of surface stickiness of a printed part in the post-curing process can be effectively solved.
The photocuring material prepared by the application is used for preparing 3D printing products, the surface of the photocuring material is basically free of stickiness, the curing rate is high, and the 3D printing products have excellent performance.
In a fifth aspect, the present application provides a method of post-curing a 3D printed article, the method comprising: and adding an active amine auxiliary agent into the aqueous solution for cleaning or soaking the 3D printing product, drying after cleaning, and performing flood exposure treatment to obtain the printing product with higher curing degree.
In the application, when an aqueous cleaning agent (such as fotoclean) is used for cleaning a printing part, a small amount of active amine auxiliary agent such as N-methyl diethanol amine can be added into the aqueous solution. During the soaking and cleaning process, the amines can be diffused inwards to a certain extent from the surface of the printing piece, and remain in a certain depth on the surface of the printing piece after the cleaning and drying are finished. In the subsequent flood post-exposure treatment, the presence of these reactive amines effectively reduces the oxygen inhibition effect, thereby promoting polymerization of the surface residual monomers and thus providing a higher cure print surface with reduced tackiness.
Compared with the prior art, the application has the following beneficial effects:
1) The application introduces monomer containing maleimide structure (preferably monomer containing benzene ring and maleimide structure) into photo-curing material, and uses its structural characteristics: the method has the advantages of excellent copolymerization reaction rate and material conversion rate, improves the Tg of the material, can absorb ultraviolet light, can reduce the transmission depth of the material, reduces the semi-solidified gel phenomenon on the surface of a workpiece, is a crystalline monomer, has a higher melting point, and is easy to crystallize because of the residual NPMI monomer on the surface of the workpiece; improved tackiness on the surface of the photocurable material article is achieved by the above structure and characteristics.
2) The reactive monomer of the application adopts acrylamide monomer, which has fast curing rate and high Tg, and can raise the glass transition temperature of the photo-curing material after the monomer participates in copolymerization, thereby further improving the stickiness of the surface of the product.
3) The end capping agent of the application adopts the (methyl) acrylamide end capping agent with hydroxyl, and after the polyurethane acrylamide oligomer synthesized by the end capping agent participates in copolymerization, the oxygen polymerization inhibition phenomenon can be overcome, the polymerization speed can be accelerated, and the stickiness phenomenon of the surface of a finished product can be further improved.
Detailed Description
The following description of the embodiments of the present application will be made in detail and without limitation, the embodiments described are only some, but not all embodiments of the present application. All other embodiments, based on the embodiments of the application, which a person of ordinary skill in the art would achieve without inventive faculty, are within the scope of the application.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the description of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.
The application provides a specific preparation method of a photo-curing material, which comprises the following steps:
the following raw materials are prepared according to the following formula:
the raw materials of the photo-curing material comprise the following components in parts by weight:
50-80 parts of polyurethane oligomer; 20-40 parts of reactive monomer; 1-10 parts of reactive photosensitive auxiliary; 0.5-3 parts of photoinitiator; wherein the reactive photosensitive aid comprises a material containing a maleimide structure; and mixing the components at normal temperature, and reacting to obtain the light-cured material.
The proportion of each component can be adjusted within the proportion range by a person skilled in the art, and the technical effect of the application can be realized.
The photocuring material prepared by adopting the mixture ratio of the components has good performance, the surface tackiness phenomenon of a product prepared by adopting the photocuring material is reduced, and the product has excellent elastic modulus, elongation at break and tensile strength.
The application adds the reactive photosensitive auxiliary agent into the raw material of the photo-curing material, and the reactive photosensitive auxiliary agent mainly comprises a material containing a maleimide structure, and the material with the structure has excellent copolymerization reaction rate and high melting point when participating in copolymerization reaction, can effectively participate in copolymerization reaction of polyurethane oligomer, improves the conversion rate of the material, improves the glass transition temperature of the material, and improves the surface stickiness phenomenon.
Specifically, the reactive photosensitive aid of the application can be specifically selected from monomer materials with phenyl groups connected in a maleimide structure.
Specifically, the application further selects a monomer with a chemical structure containing maleimide and benzene ring structure as a reactive photosensitive auxiliary agent; the benzene ring structure is selected because the benzene ring structure can absorb ultraviolet light, reduce the transmission depth of the photo-curing material, and reduce the phenomenon of semi-curing gel on the surface of a photo-curing material product so as to improve the surface stickiness.
Specifically, the application selects a monomer with a phenyl group connected to a nitrogen atom in a maleimide structure as a reactive photosensitive auxiliary agent.
Further preferred monomers which achieve the above objects of the present application are selected from at least one of N-phenylmaleimide (NPMI), N ' -4,4' -diphenylmethane Bismaleimide (BDM), N ' -m-phenylene bismaleimide (PDM) and derivatives thereof.
Even more preferably, N-phenylmaleimide (NPMI) is selected as the reactive photo-sensitive aid in the present application.
N-phenylmaleimide (NPMI) is further preferred as a reactive photosensitive aid in the present application because NPMI is a crystalline monomer having an extremely high melting point of 88-90 ℃; because NPMI is extremely easy to crystallize and has high melting point, residual NPMI monomer on the surface of a printed product can form crystals, and the surface stickiness of the material can be further improved.
Specifically, the reactive monomer of the application mainly adopts acrylamide monomer, and can specifically adopt at least one of N-vinyl pyrrolidone, N-vinyl caprolactam, N-vinyl oxazolidone, N-vinyl methyl oxazolidone and acryloylmorpholine.
The reactive monomer of the application adopts the monomer with amide structure, because the curing rate of the acrylamide monomer is high, and the acrylamide monomer has high glass transition temperature, and can effectively raise the glass transition temperature of the cured material after the acrylamide monomer participates in copolymerization, thereby further achieving the effect of improving the surface tackiness of the product.
In particular, the polyurethane oligomer of the present application is selected from polyurethane acrylate oligomers and/or polyurethane acrylamide oligomers.
Specifically, the raw materials of the polyurethane oligomer comprise the following components: isocyanate, polyol, catalyst, end-capping agent and polymerization inhibitor.
Specifically, the preparation method of the polyurethane oligomer comprises the following steps: mixing the raw materials, and reacting at 60-80 ℃ to obtain the polyurethane oligomer.
The components for synthesizing the polyurethane oligomer mainly comprise the components, and the preparation method can be selected from the prior art, so long as the method for synthesizing the polyurethane oligomer can be adopted.
Specifically, the blocking agent of the present application is selected from hydroxyl group-containing (meth) acrylamide-based blocking agents or hydroxyl group-containing (meth) acrylate blocking agents.
When the end-capping agent of the application adopts a (methyl) acrylamide-based end-capping agent monomer with hydroxyl, specifically an acrylamide monomer, the synthesized polyurethane oligomer is polyurethane acrylamide oligomer; the blocking agent monomer can overcome the problem of oxygen polymerization inhibition and stickiness, and has high polymerization speed, so that the stickiness phenomenon of the surface of the photo-curing material product can be further improved.
When the (methyl) acrylic ester end-capping agent monomer with hydroxyl is selected as the end-capping agent, the synthesized polyurethane oligomer is polyurethane acrylic ester oligomer, and the problem of stickiness of a polyurethane acrylic ester system can be improved when the polyurethane acrylic ester oligomer and the acrylamide reactive monomer are copolymerized.
Specifically, the hydroxyl-containing (meth) acrylamide-based capping agent of the present application is at least one selected from the group consisting of N- (hydroxymethyl) acrylamide, N-hydroxyethyl acrylamide, N- [ tris (hydroxymethyl) methyl ] acrylamide, and 2-hydroxypropyl methacrylamide. In addition to the above options, other hydroxyl-bearing acrylamides may be included as end-capping agents, and those skilled in the art will be able to select other end-capping agents having similar structures from the prior art.
Specifically, the (methyl) acrylic ester end-capping agent with hydroxyl is at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate and butyl ester end-capping agent. In addition to the above options, other hydroxyl-bearing acrylates endcapping agents may be included, and those skilled in the art will be able to select other endcapping agents having similar structures from the prior art.
Specifically, the photoinitiator is at least one selected from diphenyl- (2, 4, 6-trimethylbenzoyl) phosphorus oxide, phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide, ethyl 2,4, 6-trimethylbenzoyl phenylphosphonate and 2,4, 6-trimethylbenzoyl-di (p-tolyl) phosphine oxide.
Other photoinitiators may be selected from the prior art by those skilled in the art. Specifically, the raw materials of the photo-curing material also comprise antioxidants (such as 1135) and/or carbon black (N30); other types of antioxidants or fillers and the like can be selected according to actual needs.
Other raw materials matched with the components of the application can be added into the raw materials of the photo-curing material according to actual needs by a person skilled in the art so as to realize other functions.
When the photocuring material is applied to the field of 3D printing, the photocuring material has the advantages of high curing rate, excellent performance and basically no sticky phenomenon on the surface of a workpiece.
The above-described photocurable material of the present application can be used in a variety of fields, not limited to 3D printing materials.
The application prepares a 3D printing product by using the light-cured material; the surface of the product is basically free from stickiness, the curing speed is high, and the 3D printing product has excellent performance.
When the printing piece is placed in water for post-curing reaction, active hydrogen containing amines in the reactive monomer, the end capping agent and the reactive photosensitive auxiliary agent in the photo-curing raw material can be used as an electron donor, so that the free radical annihilated by oxygen can be promoted to restore activity, and the problem of surface stickiness of the printing piece in the post-curing process can be effectively solved.
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
Unless otherwise indicated, all starting materials in the examples of the present application were purchased commercially.
Unless otherwise indicated, conventional testing methods or instrumental recommended testing methods are employed.
Example 1 (preparation of urethane acrylate oligomer)
The synthesis process comprises the following steps: 444.6g of isophorone diisocyanate (IPDI) and 12000g of polypropylene glycol dihydric alcohol (PPG 12000, molecular weight is 12000) are added into a reaction bottle according to a proportion, the temperature is slowly raised, the temperature is controlled to be 50-60 ℃, 3.80g of dibutyltin dilaurate (DBTDL) is dropwise added, after the dropwise addition is completed, the temperature is raised to 80 ℃, 6.34g of para-hydroxyanisole (MEHQ) is added, 234.56g of hydroxyethyl acrylate (HEA) is dropwise added, the temperature is controlled to be 80 ℃, and stirring reaction is carried out; and detecting the reaction system in an infrared spectrum to completely react NCO groups to obtain the polyurethane acrylate oligomer, namely PPG-037.
Example 2 (preparation of polyurethane acrylamide oligomer)
The synthesis process comprises the following steps: 444.6g of isophorone diisocyanate (IPDI) and 12000g of polypropylene glycol dihydric alcohol (PPG 12000, molecular weight is 12000) are added into a reaction bottle according to a proportion, the temperature is slowly raised, the temperature is controlled to be 50-60 ℃, 3.80g of dibutyltin dilaurate (DBTDL) is dropwise added, after the dropwise addition is completed, the temperature is raised to 80 ℃, 6.34g of para-hydroxyanisole (MEHQ) is added, 232.60g N-hydroxyethyl acrylamide (HEAA) is dropwise added, the temperature is controlled to be 80 ℃, and stirring reaction is carried out; and detecting the reaction system in an infrared spectrum to completely react NCO groups to obtain the polyurethane acrylamide oligomer, which is marked as PPG-040.
Example 3 (preparation of photocurable Material)
The synthesis process comprises the following steps: mixing a photoinitiator 819, an antioxidant 1135, a reactive monomer NVP (N-vinyl pyrrolidone), N-phenyl maleimide (NPMI), a polyurethane acrylate oligomer PPG-037 (prepared in example 1) and black N30 (carbon black 30), and stirring and mixing at normal temperature to obtain a photo-curing resin material; the composition in parts by weight is shown in Table 1.
Example 4 (preparation of photocurable Material)
The synthesis process comprises the following steps: mixing a photoinitiator 819, an antioxidant 1135, a reactive monomer NVP (N-vinyl pyrrolidone), N-phenyl maleimide (NPMI), a polyurethane acrylamide oligomer PPG-040 (prepared in example 2) and black N30 (carbon black 30), and stirring and mixing at normal temperature to obtain a photo-curing resin material; the composition in parts by weight is shown in Table 1.
Example 5 (preparation of photocurable Material)
The synthesis process comprises the following steps: mixing a photoinitiator 819, an antioxidant 1135, a reactive monomer NVP (N-vinyl pyrrolidone), N-phenyl maleimide (NPMI), a polyurethane acrylate oligomer PPG-037 (prepared in example 1) and black N30 (carbon black 30), and stirring and mixing at normal temperature to obtain a photo-curing resin material; the composition in parts by weight is shown in Table 1.
Example 6 (preparation of photocurable Material)
The synthesis process comprises the following steps: mixing a photoinitiator 819, an antioxidant 1135, a reactive monomer IBOA (isobornyl acrylate), N-phenyl maleimide (NPMI), a polyurethane acrylate oligomer PPG-037 (prepared in example 1) and black N30 (carbon black 30), and stirring and mixing at normal temperature to obtain a photo-curing resin material; the composition in parts by weight is shown in Table 1.
Comparative example 1 (preparation of photocurable material)
Comparative example 1 differs from example 3 in that N-phenylmaleimide (NPMI) was not included in the synthetic raw material; the specific formulation is shown in Table 1.
Comparative example 2 (preparation of photocurable material)
Comparative example 2 differs from example 4 in that N-phenylmaleimide (NPMI) was not included in the synthetic raw material; the specific formulation is shown in Table 1.
The liquid photo-curing materials of examples 3 to 6 and comparative examples 1 to 2 were used, dog-bone shaped tensile test bars of Die C type were printed by LEAP technique according to ASTM D412, post-treated (after immersing the printed article in aqueous solution, an active amine auxiliary agent was added to the aqueous solution to increase the curing degree, dried after washing was completed, and subjected to flood exposure treatment to obtain a printed article having a higher curing degree), mechanical properties after curing of the 6 materials were tested by an Instron 34TM-10 universal material tester, and sensory evaluation was performed on the surface tackiness of the printed article, and the test results are shown in Table 2.
TABLE 1 photo-curable material formulation tables of comparative examples 1-2 and examples 3-6
TABLE 2 3D Performance test Table for 3D articles printed with photo-curable materials of comparative examples 1-2 and examples 3-6
The degree of tackiness in Table 2 was evaluated by artificial sensory, and a lower number, on the scale of 1-5, represents a higher surface viscosity of the print (a professional surface tack test instrument may also be used).
Tack score: according to the application, 100 persons skilled in the art are invited to touch and press the surfaces of the 6 3D printing products by hand, sense different stickiness degrees of the surfaces of the products, and give a score of 1-5; the tack degree scores of the above 6 3D printed products were obtained after comprehensive evaluation and are shown in table 2.
Table 2 shows: comparative example 1 was about 3 minutes, comparative example 2 was about 4 minutes, example 3 was about 4.5 minutes, example 4 was about 5 minutes, example 5 was about 5 minutes, and example 6 was about 4.5 minutes.
By comparison, it can be seen that: the surface tackiness of the 3D product printed by the photo-curing material is scored at 4.5-5, and the score of comparative examples 1-2 is scored at 3-4, so that the surface tackiness of the product is obviously reduced, and the curing degree is better.
Inventive example 3 differs from comparative example 1 in that N-phenylmaleimide was added to the inventive photocurable material, whereas comparative example 1 was not added; comparison of the viscosity scores shows that: the surface tackiness of the 3D printing product is obviously reduced, which indicates that the photocuring material has better curing effect; it was further verified that the introduction of N-phenylmaleimide into the raw material of the photocurable material can improve the curing effect or curing rate of the photocurable material.
Likewise, example 4 of the present application differs from comparative example 2 in that N-phenylmaleimide was added to the photocurable material of the present application, whereas comparative example 2 was not added; comparison of the viscosity scores shows that: the surface tackiness of the 3D printing product is obviously reduced, which indicates that the photocuring material has better curing effect; it was further verified that the incorporation of N-phenylmaleimide into photocurable materials can enhance the curing effect of the photocurable materials and improve the problem of tackiness on the surface of the articles.
Comparative example 1 differs from comparative example 2 in that the oligomer of the photocurable material of comparative example 1 is a urethane acrylate oligomer and the oligomer of the photocurable material of comparative example 2 is a urethane acrylamide oligomer; comparison of the viscosity scores shows that: comparative example 2 the 3D article printed with the photocurable material selected for polyurethane acrylamide oligomer had a higher surface tack score than comparative example 1; it is further verified that the introduction of the urethane acrylamide oligomer into the photocurable material can further improve the curing effect of the photocurable material and improve the problem of tackiness on the surface of the product.
Likewise, example 3 differs from example 4 in that the polyurethane oligomer selected is different; comparison of the viscosity scores shows that: example 2 the 3D article printed with the photocurable material selected for polyurethane acrylamide oligomer had a higher surface tack score than example 1; it has been further verified that the introduction of the urethane acrylamide oligomer into the photocurable material can further enhance the curing effect of the photocurable material and improve the problem of tackiness on the surface of the article.
By comparing the tackiness of the above-mentioned comparative examples 1 and 2, examples 3 and 4, it was indirectly confirmed that the use of a hydroxyl group-containing (meth) acrylamide-based blocking agent as the blocking agent in the urethane oligomer can increase the curing rate of the photocurable material and improve the tackiness problem on the surface of the article.
Example 5 differs from example 6 in that the reactive monomer of example 5 is NVP (N-vinylpyrrolidone) and the reactive monomer of example 6 is IBOA (isobornyl acrylate); whereas the viscosity score of example 5 is higher than that of example 6; by comparison, it can be seen that: the NVP (N-vinyl pyrrolidone) acrylamide monomer is selected in the photo-curing material, so that the curing rate of the photo-curing material can be improved, and the problem of tackiness on the surface of the product can be solved.
3D printed article performance test results:
from the test data in Table 2, the modulus of elasticity, tensile strength, and elongation at break of the 3D articles printed with the photocurable materials of comparative example 1 and comparative example 2 are all significantly less than the properties of the 3D articles printed with the photocurable materials of the present application.
The photocurable materials of examples 3-6 of the present application are different from comparative examples 1-2 in the ratio of the reactive monomers, and N-phenylmaleimide was added; it is known that the proportion of each component of the photo-curing material affects the performance, the selection of the preferred formula of the application can improve the comprehensive performance of the photo-curing material, and the addition of the N-phenyl maleimide reactive photosensitive auxiliary agent can improve the stickiness problem and the comprehensive mechanical property of the material.
Comparative example 1 and comparative example 2, since different polyurethane oligomers were selected to synthesize the photo-curing materials, the mechanical properties of the two materials can be shown: in comparative example 2, the polyurethane acrylamide oligomer is adopted, so that the comprehensive mechanical properties of the product are obviously higher than those of the photo-curing material printing product synthesized by the polyurethane acrylate oligomer; further, it is verified that the polyurethane acrylamide oligomer selected in the photo-curing material can not only improve the problem of stickiness of the surface of the product, but also improve the comprehensive mechanical property of the product.
Similarly, the test results of examples 3 and 4 further demonstrate that the use of polyurethane acrylamide oligomers in the photocurable material not only improves the surface tackiness problem of the article, but also improves the overall mechanical properties of the article.
Example 5 and example 6 due to the different reactive monomers used now, it is known by the mechanical properties of both: example 5 since NVP (N-vinyl pyrrolidone) monomer was selected, the comprehensive mechanical properties of the product were significantly higher than those of the photo-curable material print product synthesized from IBOA (isobornyl acrylate) reactive monomer; further, it is verified that the NVP (N-vinyl pyrrolidone) acrylamide monomer selected in the photo-curing material can not only improve the problem of product surface stickiness, but also improve the comprehensive mechanical properties of the product.
The application introduces monomer containing maleimide structure (preferably monomer containing benzene ring and maleimide structure) into photo-curing material, and uses its structural characteristics: the method has the advantages of excellent copolymerization reaction rate and material conversion rate, improves the Tg of the material, can absorb ultraviolet light, can reduce the transmission depth of the material, reduces the semi-solidified gel phenomenon on the surface of a workpiece, is a crystalline monomer, has a higher melting point, and is easy to crystallize because of the residual NPMI monomer on the surface of the workpiece; improved tackiness on the surface of the photocurable material article is achieved by the above structure and characteristics.
The reactive monomer of the application adopts acrylamide monomer, which has fast curing rate and high Tg, and can raise the glass transition temperature of the photo-curing material after the monomer participates in copolymerization, thereby further improving the stickiness of the surface of the product.
The end capping agent of the application adopts the (methyl) acrylamide end capping agent with hydroxyl, and after the polyurethane acrylamide oligomer synthesized by the end capping agent participates in copolymerization, the oxygen polymerization inhibition phenomenon can be overcome, the polymerization speed can be accelerated, and the stickiness phenomenon of the surface of a finished product can be further improved.
According to the application, N-phenylmaleimide is introduced into the photo-curing material as a reactive photosensitive auxiliary agent, an acrylamide reaction monomer, a hydroxyl-containing (methyl) acrylamide end capping agent and an optimized proportioning relationship of the components in the raw materials are selected, so that the comprehensive mechanical property of the 3D printing product of the photo-curing material is improved, and the phenomenon of stickiness on the surface of the product is improved.
In the technical scheme, the maleimide monomer is used as a main influencing factor, the amide reactive monomer and the (methyl) acrylamide end capping agent with hydroxyl are used as auxiliary influencing factors, and the aims of improving the stickiness problem and the comprehensive mechanical property are jointly achieved by combining the raw material proportion, so that the effect is remarkable.
While the application has been described in terms of preferred embodiments, it will be understood by those skilled in the art that various changes and modifications can be made without departing from the scope of the application, and it is intended that the application is not limited to the specific embodiments disclosed.
Claims (10)
1. The light-cured material is characterized by comprising the following raw materials in parts by weight:
wherein the monomer structure of the reactive photosensitive additive comprises a maleimide structure.
2. A photocurable material according to claim 1, wherein a phenyl group is attached to said maleimide structure.
3. A photocurable material according to claim 1, wherein the nitrogen atom of the maleimide structure is bonded to a phenyl group.
4. A photocurable material according to claim 1, wherein the reactive photoactive aid is selected from at least one of N-phenylmaleimide (NPMI), N ' -4,4' -diphenylmethane Bismaleimide (BDM), N ' -m-phenylene bismaleimide (PDM), and derivatives thereof.
5. A photocurable material according to claim 1, wherein said reactive monomer is selected from at least one of N-vinyl pyrrolidone, N-vinyl caprolactam, N-vinyl oxazolidone, N-vinyl methyl oxazolidone, acryloylmorpholine;
preferably, the polyurethane oligomer is selected from polyurethane acrylate oligomers and/or polyurethane acrylamide oligomers.
6. A photocurable material according to claim 1, characterized in that the raw materials of said polyurethane oligomer comprise the following components: isocyanate, polyol, catalyst, end-capping agent and polymerization inhibitor; wherein the blocking agent is selected from hydroxyl-containing (meth) acrylamide-based blocking agents or hydroxyl-containing (meth) acrylate blocking agents.
7. The photocurable material of claim 6, wherein said hydroxyl-containing (meth) acrylamide-based capping agent is selected from at least one of N- (hydroxymethyl) acrylamide, N-hydroxyethyl acrylamide, N- [ tris (hydroxymethyl) methyl ] acrylamide, 2-hydroxypropyl methacrylamide;
preferably, the (methyl) acrylic ester end-capping agent with hydroxyl is at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate and butyl ester end-capping agent;
preferably, the photoinitiator is selected from at least one of diphenyl- (2, 4, 6-trimethylbenzoyl) oxyphosphine, phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide, ethyl 2,4, 6-trimethylbenzoyl phenylphosphonate, 2,4, 6-trimethylbenzoyl-di (p-tolyl) phosphine oxide.
8. A method for producing a photocurable material according to any one of claims 1-7, characterized in that said method comprises the steps of:
s1: preparing raw materials according to a raw material formula;
s2: and stirring and mixing the polyurethane oligomer, the reactive monomer, the reactive photosensitive auxiliary and the photoinitiator to obtain the light-cured material.
9. Use of the photocurable material according to any one of claims 1-7 in a 3D printing material.
10. A 3D printed article, characterized in that the material of the 3D printed article comprises the photocurable material according to any one of claims 1-7.
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